CN110616055B - Water-based binder and preparation method and application thereof - Google Patents
Water-based binder and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H—ELECTRICITY
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Abstract
The invention provides a water-based adhesive, which is water-soluble reinforced polyvinyl alcohol grafted with polyacrylic acid long-chain branches or copolymerization and long-chain branches of acrylic acid monomers and olefin monomers. The aqueous binder overcomes the defects of easy peeling and air entraining when polyvinyl alcohol is used for dispersing slurry, and the preparation method accurately introduces long-chain branches, improves the cycle performance of the high-gram-capacity silicon-based negative electrode, and obviously inhibits the expansion of a pole piece.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, relates to an electrode material of a lithium ion secondary battery, and particularly relates to a water-based adhesive, and a preparation method and application thereof.
Background
In order to solve the problems of deformation, deterioration, and the like of a battery due to the cyclic volume expansion of a non-carbonaceous negative electrode active material, a binder having high bonding strength and capable of uniformly dispersing expansion stress has been developed to realize the cyclic stability of a high-capacity non-carbonaceous active material negative electrode. On the other hand, because of the enhanced awareness of environmental protection, battery manufacturers prefer to use a water-based binder as a lithium ion battery negative electrode binder.
CN 101361212A discloses a polyvinyl alcohol adhesive with a polymerization degree of more than 2500 and a saponification degree of more than 90%, but the research of the inventor proves that the polyvinyl alcohol which is not modified by water solubility enhancement has poor dispersion performance to slurry when used as the adhesive, the polyvinyl alcohol is easy to cause surface skinning and air entrainment of the slurry when dispersed at high speed, the performance of the silicon-based negative pole piece is influenced, and the pole piece expands after charge-discharge circulation. On the other hand, the topological structure of the polyvinyl alcohol polymer chain is a linear structure, in the pole piece, the addition amount of the adhesive is low, the physical entanglement effect among polymer molecular weights is weak, and the acting sites among molecules are few, so that the effect of the adhesive on uniform dispersion expansion force is poor.
CN 102412401A shows high cohesive force and improves battery cycle performance by introducing certain alkali metal hydroxide neutralized polyacrylic acid and polyvinyl alcohol to compound and cross-link at high temperature as the adhesive of silicon-based negative electrode, but such an adhesive is brittle per se and is not beneficial to pole piece processing. CN 101507020A uses polyvinyl alcohol and polyurethane to prepare semi-interpenetrating network adhesive as silicon-based cathode adhesive, shows better cohesive force, has good electrolyte resistance and improved tensile property, and improves the capacity or power output performance of the battery. CN 101529625 a is used as a binder of silicon-based or tin-based negative electrode material by compounding polyvinyl alcohol with polymerization degree of more than 3000 and saponification degree of more than 80% and polyvinylpyrrolidone, thereby reducing swelling of the electrode sheet.
CN 104247088A is copolymerized and alcoholyzed by vinyl acetate and acrylic acid to obtain carboxyl modified polyvinyl alcohol, which improves the heat resistance of the polyvinyl alcohol and is used as the adhesive of the secondary battery diaphragm ceramic powder. CN 101260282A adopts polyvinyl alcohol or acetal derivatives thereof as main polymers, adopts two or more than two different polar monomers as graft copolymers to prepare high-viscosity emulsion and uses the emulsion as a positive electrode adhesive of a battery, thereby solving the problems of low compacted density of the positive electrode and brittleness of a dried pole piece.
CN 105914377 a prepares an aqueous binder with a multi-branched structure by performing michael addition reaction or graft copolymerization on a biomass water-soluble polymer or a synthetic water-soluble polymer, but the graft reaction or michael addition reaction is very likely to cause degradation of the biomass water-soluble polymer. On the other hand, the synthetic water-soluble polymer is adopted to avoid the defects, but the grafting density and the grafting chain length cannot be controlled due to the low grafting efficiency of the material. CN 105958075A takes polyvinyl alcohol as a substrate, and takes hydrophilic monomers and lipophilic monomers to prepare a multi-element functional modified polyvinyl alcohol aqueous binder through Michael addition modification. However, it is worth mentioning that the presence of residual small molecule monomers after Michael addition modification has a large impact on slurry dispersion and binder performance.
However, no aqueous binder particularly suitable for silicon-based negative electrodes has been found in the market.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a water-based binder, a preparation method and an application thereof, wherein the water-based binder overcomes the defects of easy peeling and air entraining when polyvinyl alcohol is used for dispersing slurry, and the preparation method accurately introduces long-chain branches, improves the cycle performance of a high-gram-capacity silicon-based negative electrode and obviously inhibits the expansion of a pole piece.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a water-based adhesive which is water-soluble reinforced polyvinyl alcohol grafted with polyacrylic acid long-chain branches or copolymerization and long-chain branches of acrylic acid monomers and olefin monomers.
As a preferred embodiment of the present invention, the olefin monomer includes any one of or a combination of at least two of a sulfonic acid group alkenyl monomer, a carboxyl group alkenyl monomer, or an amino group alkenyl monomer, and typical but non-limiting examples of the combination are: a combination of a sulfonic acid alkenyl monomer and a carboxyl alkenyl monomer, a combination of a carboxyl alkenyl monomer and an amino alkenyl monomer, a combination of an amino alkenyl monomer and a sulfonic acid alkenyl monomer, or a combination of a sulfonic acid alkenyl monomer, a carboxyl alkenyl monomer and an amino alkenyl monomer, and the like.
Preferably, the sulfonic acid group alkenyl monomer includes any one of sodium styrene sulfonate, sodium vinyl sulfonate, sodium allyl sulfonate, sodium 2-methallyl sulfonate, sodium ethyl methacrylate sulfonate or 2-acrylamide-2-methylpropanesulfonic acid or a combination of at least two thereof, which are typical but non-limiting examples of the combination: combinations of sodium styrene sulfonate and sodium vinyl sulfonate, combinations of sodium vinyl sulfonate and sodium allyl sulfonate, combinations of sodium allyl sulfonate and sodium 2-methallyl sulfonate, combinations of sodium 2-methallyl sulfonate and sodium ethyl methacrylate sulfonate, combinations of sodium ethyl methacrylate sulfonate or 2-acrylamide-2-methylpropanesulfonic acid, or combinations of sodium vinyl sulfonate, sodium allyl sulfonate and sodium 2-methallyl sulfonate, and the like.
Preferably, the carboxyl alkenyl monomer comprises any one of fumaric acid, methacrylic acid, itaconic acid or monobutyl itaconate, or a combination of at least two of these, typical but non-limiting examples being: combinations of fumaric acid and methacrylic acid, methacrylic acid and itaconic acid, itaconic acid and monobutyl itaconate, monobutyl itaconate and fumaric acid, or fumaric acid, methacrylic acid and itaconic acid, and the like.
Preferably, the aminoalkenyl monomer comprises any one of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide, or a combination of at least two of these, typical but non-limiting examples being: combinations of acrylamide and methacrylamide, methacrylamide and N-methylolacrylamide, N-methylolacrylamide and N, N-dimethylacrylamide, N-dimethylacrylamide and acrylamide, or acrylamide, methacrylamide, and N-methylolacrylamide, and the like.
As a preferable technical scheme of the invention, the waterborne reinforced polyvinyl alcohol is obtained by reacting polyvinyl alcohol with a compound A, wherein the structure of the compound A is shown as a formula I:
wherein R is 1 Is absent or is a linear or branched alkylene group of C1-C4, R 2 Is amino, hydroxyl,
The linear or branched alkylene group having 1 to 4 may be any of linear or branched alkylene groups having 1, 2, 3, or 4.
The continuous functionalization modified high-water-solubility polyvinyl alcohol with the long-chain branch chain can be used for efficiently dispersing slurry, and is free of skinning and air-entraining under a long-time dispersion condition. As a high gram capacity silicon-based negative electrode aqueous binder, the swelling can be obviously inhibited, and the cycle performance is improved.
The second object of the present invention is to provide a method for preparing the above water-soluble binder, comprising the steps of:
(1) mixing the polyvinyl alcohol solution with an aqueous solution of an alkaline substance, adding the compound A for reaction, and cooling to obtain a water-solubility-enhanced polyvinyl alcohol solution;
(2) mixing the water-soluble enhanced polyvinyl alcohol solution obtained in the step (1) with a compound B and an acrylic monomer or a composition of the acrylic monomer and an olefin monomer for reaction, adding an initiator and continuing to react to obtain a water-based binder;
wherein the structure of the compound B is shown as a formula II:
R 3 is phenyl or methyleneoxy.
Wherein when R is 3 In the case of a phenyl group, the positional relationship between the ethylene oxide group and the vinyl group bonded to the phenyl group may be any of ortho, meta or para.
In a preferred embodiment of the present invention, the polymerization degree of the polyvinyl alcohol in the step (1) is 100 to 8000, such as 100, 200, 500, 800, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, etc., but the polymerization degree is not limited to the above-mentioned values, and other values not listed in the above-mentioned value range are also applicable, and preferably 1000 to 6000.
Preferably, the degree of alcoholysis of the polyvinyl alcohol of step (1) is 60 to 99.99%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99%, but not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 80 to 99.99%.
Preferably, the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol solution in step (1) is 5-45%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the alkaline substance in step (1) is lithium hydroxide and/or sodium hydroxide.
Preferably, the mass fraction of the alkaline substance in the alkaline substance aqueous solution in step (1) is 0.1-15%, such as 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, or 15%, but not limited to the recited values, and other non-recited values within the range of the values are also applicable.
Preferably, the molar ratio of the basic substance to the polyvinyl alcohol monomer in step (1) is (0.005-10): 1, such as 0.005:1, 0.01:1, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the temperature of the mixing in step (1) is 25 to 60 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing of step (1) is carried out under stirring.
Preferably, the stirring time is 0.5 to 3 hours, such as 0.5 hour, 1 hour, 1.5 hour, 2 hours, 2.5 hours, or 3 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the molar ratio of the compound a to the polyvinyl alcohol monomer in the step (1) is (0.005 to 100: 1), for example, 0.005:1, 0.01:1, 0.1:1, 0.5:1, 1:1, 10:1, 20:1, 50:1, 80:1, 90:1 or 100:1, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the reaction temperature in step (1) is 60 to 90 ℃, such as 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time in step (1) is 0.5-10 h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the temperature in step (1) is reduced to 30-60 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
In a preferred embodiment of the present invention, the molar ratio of the compound B to the polyvinyl alcohol monomer in the step (2) is (0.0005 to 10: 1), for example, 0.0005:1, 0.001:1, 0.01:1, 0.1:1, 0.5:1, 1:1, 2:1, 5:1, 8:1 or 10:1, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the molar ratio of the acrylic monomer or acrylic monomer and olefin monomer composition to polyvinyl alcohol monomer in step (2) is (0.003-80): 1, such as 0.003:1, 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1 or 80:1, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the mass of the acrylic monomer and the acrylic monomer in the olefin monomer composition in step (2) is 0.1 to 100% of the total mass of the composition, excluding 100%, such as 0.1%, 0.2%, 0.5%, 1%, 2%, 5%, 8%, 10%, 20%, 50%, 80%, 90% or 99%, but not limited to the enumerated values, and other non-enumerated values in the range of the enumerated values are also applicable.
Preferably, the temperature of the mixing reaction in step (2) is 30 to 60 ℃, such as 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the mixing reaction time in step (2) is 0.5-6 h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the initiator in the step (2) is an inorganic peroxide initiator and/or a redox initiator.
Preferably, the inorganic peroxide initiator comprises any one of, or a combination of at least two of, ammonium persulfate, sodium persulfate or potassium persulfate, typical but non-limiting examples of which are: a combination of ammonium persulfate and sodium persulfate, a combination of sodium persulfate and potassium persulfate, a combination of potassium persulfate and ammonium persulfate, or a combination of ammonium persulfate, sodium persulfate and potassium persulfate, or the like.
Preferably, the redox initiator is a combination of ammonium persulfate and sodium sulfite or a combination of ammonium persulfate and sodium bisulfite.
Preferably, the initiator of step (2) is added in an amount of 0.0001 to 1.5% by mass of the olefinic acid monomer or the acrylic acid monomer and olefin monomer composition, such as 0.0001%, 0.001%, 0.01%, 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, or 1.5%, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred embodiment of the present invention, the temperature for continuing the reaction after adding the initiator in the step (2) is 30 to 90 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reaction time after the initiator is added in step (2) is 0.5-18 h, such as 0.5h, 1h, 2h, 5h, 8h, 10h, 12h, 15h or 18h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
The invention also aims to provide the application of the aqueous binder, and the aqueous binder is used for preparing the lithium ion battery.
According to the invention, a continuous functionalization method is adopted, firstly, water-solubility enhancement modification is carried out on polyvinyl alcohol, then double bond functionalization is carried out on a main chain, finally, acrylic acid is taken as a first comonomer and is graft copolymerized with other olefin monomers to prepare the water-soluble polyvinyl alcohol-based water-based binder with a long branched chain structure, the long branched chain structure of the binder enhances physical entanglement among polymer molecular chains of the binder under a low timely adding amount of the binder in a pole piece, and acting force sites among the molecular chains are increased, so that the water-based binder disclosed by the invention has excellent dispersion performance and uniform dispersion expansibility, and is particularly suitable for a silicon-based negative electrode binder.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the invention provides a water-based binder, which overcomes the defects of easy peeling and air entraining when polyvinyl alcohol is used for dispersing slurry, improves the cycle performance of a high-gram-capacity silicon-based negative electrode, remarkably inhibits the expansion of a pole piece, and has a capacity retention rate of about 90% at 50 weeks and an expansion rate of about 60% at 50 weeks;
(2) the invention provides a preparation method of a water-based binder, which is simple and suitable for industrial production, and long-chain branches are accurately introduced into polyvinyl alcohol molecules.
Drawings
FIG. 1 is an SEM image of a battery pole piece prepared by using the aqueous binder prepared in example 1 of the invention;
fig. 2 is an SEM image of a battery electrode sheet prepared using the aqueous binder prepared in comparative example 1 of the present invention.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
A method of preparing an aqueous binder, the method comprising the steps of:
(1) adding 80g of polyvinyl alcohol (1.81mol, polymerization degree of 3000 and alcoholysis degree of 99%) into 320g of deionized water, heating to 90 ℃, stirring and dissolving for 0.5h, cooling to 40 ℃, mixing with 70g of 20% by mass sodium hydroxide aqueous solution (0.35mol), stirring and mixing for 1h, adding 50g of 60% by mass acrylamide aqueous solution for reaction (0.42mol), heating to 70 ℃, preserving heat for reaction for 4h, and cooling to 60 ℃ to obtain a polyvinyl alcohol solution with enhanced water solubility;
(2) and (2) stirring, mixing and reacting the water-soluble enhanced polyvinyl alcohol solution obtained in the step (1) with 4g of allyl glycidyl ether (0.035mol) and 22.7g of acrylic acid (0.315mol) for 1h, adding 0.54g of ammonium persulfate aqueous solution with the mass fraction of 5%, and continuing to react for 10h at the temperature of 60 ℃ to obtain light yellow viscous liquid, namely the water-based adhesive.
Example 2
A method for producing an aqueous binder, which is the same as in example 1 except that 22.7g of acrylic acid was replaced with 15g of acrylic acid and 22.1g of 2-acrylamido-2-methylpropanesulfonic acid.
Example 3
A process for the preparation of an aqueous binder, which process is identical to that of example 1, except that 22.7g of acrylic acid is replaced by 15g of acrylic acid and 19.88g of monobutyl itaconate.
Example 4
A method of preparing an aqueous binder, the method comprising the steps of:
(1) adding 80g of polyvinyl alcohol (1.81mol, the polymerization degree is 2500, and the alcoholysis degree is 99%) into 320g of deionized water, heating to 90 ℃, stirring and dissolving for 0.5h, cooling to 40 ℃, mixing with 100g of a 30% sodium hydroxide aqueous solution (0.75mol) under stirring for 1h, adding 89.2g of a 60% acrylamide aqueous solution under stirring for reaction (0.75mol), heating to 70 ℃, preserving heat for reaction for 4h, and cooling to 60 ℃ to obtain a polyvinyl alcohol solution with enhanced water solubility;
(2) stirring and mixing the polyvinyl alcohol solution with enhanced water solubility obtained in the step (1), 4g of allyl glycidyl ether (0.035mol) and 48.7g of acrylic acid (0.675mol) for reaction for 1h, adding 1.16g of ammonium persulfate aqueous solution with the mass fraction of 5%, stirring and reacting for 10h at 60 ℃, and obtaining yellow viscous liquid, namely the water-based adhesive.
Example 5
A process for the preparation of an aqueous binder, which process is identical with that of example 4, except that 1g of allyl glycidyl ether is added.
Example 6
A method of preparing an aqueous binder, which is the same as in example 4 except that the amount of polyvinyl alcohol was increased to 120 g.
Example 7
A method of preparing an aqueous binder, the method comprising the steps of:
(1) adding 80g of polyvinyl alcohol (1.81mol, 100 degree of polymerization and 60 percent of alcoholysis) into 320g of deionized water, heating to 90 ℃, stirring and dissolving for 0.5h, cooling to 25 ℃, mixing with 100g of 30 percent lithium hydroxide aqueous solution (1.5mol), stirring and mixing for 1h, adding 152.5g of 60 percent 3-acrylamide-2-methylpropanesulfonic acid aqueous solution for reaction (0.5mol), heating to 60 ℃, keeping the temperature for reaction for 10h, and cooling to 30 ℃ to obtain the polyvinyl alcohol solution with enhanced water solubility;
(2) stirring, mixing and reacting the polyvinyl alcohol solution with enhanced water solubility obtained in the step (1) with 7.3g of p-ethylene oxide styrene (0.05mol), 48.7g of acrylic acid (0.675mol) and 11.6g of fumaric acid (0.1mol) for 6h, adding 1.5g of sodium persulfate aqueous solution with the mass fraction of 5%, stirring and reacting at 30 ℃ for 18h to obtain yellow viscous liquid, namely the water-based adhesive.
Example 8
A method of preparing an aqueous binder, the method comprising the steps of:
(1) adding 100g of polyvinyl alcohol (2.27mol, 8000 degree of polymerization and 80 percent of alcoholysis) into 320g of deionized water, heating to 90 ℃, stirring and dissolving for 0.5h, cooling to 25 ℃, mixing with 100g of 20 percent by mass sodium hydroxide aqueous solution (0.5mol), stirring and mixing for 1h, adding 281.7g of 60 percent by mass 3-acrylamidopropanesulfonic acid aqueous solution for reaction (1mol), heating to 90 ℃, preserving heat for reaction for 0.5h, and cooling to 60 ℃ to obtain a polyvinyl alcohol solution with enhanced water solubility;
(2) stirring, mixing and reacting the polyvinyl alcohol solution with enhanced water solubility obtained in the step (1) with 14.6g of o-ethylene oxide styrene (0.1mol), 48.7g of acrylic acid (0.675mol) and 17.2g of methacrylamide (0.2mol) for 0.5h, adding 1.5g of potassium persulfate aqueous solution with the mass fraction of 5%, and stirring and reacting at 90 ℃ for 0.5h to obtain yellow viscous liquid, namely the water-based binder.
Comparative example 1
A method of preparing an aqueous binder, which is the same as that of example 4, except that polyvinyl alcohol having a polymerization degree of 2500 and an alcoholysis degree of 99% was used without modifying the water solubility to be enhanced.
Comparative example 2
A method for preparing an aqueous binder using the water-soluble modified polyvinyl alcohol prepared in example 1 alone as a binder for a lithium ion battery.
Comparative example 3
A method for preparing an aqueous binder, which method is the same as in example 1 except that allyl glycidyl ether is not added.
Comparative example 4
Cell performance was evaluated using a commercially available CMC/SBR system as the binder set.
The aqueous binders prepared in examples 1 to 8 and comparative examples 1 to 4 were investigated for slurry dispersibility. The water-based adhesives prepared in examples 1 to 8 and comparative examples 1 to 4 were used to prepare pole pieces of motors, and the peel strength, flexibility and electrochemical properties of the pole pieces were tested according to the following test methods, and the results are shown in table 1.
Manufacturing a battery pole piece:
the adhesive described in the above examples and comparative examples was used for the fabrication of silicon-based/graphite composite negative electrode material electrode sheets.
As the silicon-based/graphite composite negative electrode material, SiO is preferred x the/C or Si-C composite material containing Si and C is prepared by compounding natural graphite or artificial graphite.
According to the invention, a silicon-based/graphite composite anode material with gram capacity of 600mAh/g is preferably used.
The mass fraction of the silicon-based composite negative electrode material is 92.0 wt%, the mass fraction of the conductive carbon black is 4.0 wt%, and the mass fraction of the aqueous binder (marked as L-PVA) in the embodiment is 4 w% in terms of solid content, and a proper amount of deionized water is added according to the proportion that the total solid content is 45% to prepare the battery pole piece slurry. The slurry was passed through a 100-mesh screen, coated on a 10 μm thick copper foil as a current collector, dried at 120 ℃ for 5 minutes, and then dried at room temperature at a temperature of 10X 10 4 Load per unit length of N/mRolling to obtain the electrode plate.
Measurement of peel strength: the electrode sheets of examples and comparative examples were cut into a 20cm × 2.5cm long strip, a steel sheet 1mm thick was adhered to the collector side with a double-sided tape, a transparent adhesive tape was adhered to the coated layer side, and the sheet was peeled in a 180 ° direction at a speed of 100mm/min with a tensile tester, and the peel stress was measured.
Slurry dispersion study: the dispersed slurries of examples and comparative examples were allowed to stand to observe the surface morphology of the slurries, and the skinned state was marked as X, and the smoothness of the slurries was marked as "" uniform "". Slurry bleed was recorded as ×, slurry no bubbles or very small amounts as ×.
Evaluating the flexibility of the pole piece: a mandrel with the diameter phi of 3mm is placed on one side of the current collector of the rolled pole piece in the examples and the comparative examples, bending experiments are carried out, the state of the pole piece at the moment is observed through an optical microscope, the pole piece is good and marked as O, and the pole piece is marked as X when falling or cracking occurs.
Evaluation of battery performance: and (3) preparing the pole piece into a simulated battery, testing the initial coulombic efficiency of charge-discharge circulation and the coulombic efficiency and the capacity retention rate after 50 times of circulation by adopting a constant current method, and recording the ratio of the thickness increase value of the pole piece in a lithium-embedded state of the pole piece to the thickness of the pole piece before charge and discharge as the pole piece expansion rate (%) after 50 times of charge-discharge circulation.
TABLE 1
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (28)
1. The water-based adhesive is characterized in that the adhesive is water-soluble reinforced polyvinyl alcohol grafted with polyacrylic acid branched chains or copolymerization and branched chains of acrylic acid monomers and olefin monomers;
the aqueous binder is prepared by a process comprising the steps of:
(1) mixing the polyvinyl alcohol solution with an aqueous solution of an alkaline substance, adding the compound A for reaction, and cooling to obtain a water-solubility-enhanced polyvinyl alcohol solution;
(2) mixing the water-soluble enhanced polyvinyl alcohol solution obtained in the step (1) with a compound B and an acrylic monomer or a composition of the acrylic monomer and an olefin monomer for reaction, adding an initiator and continuing to react to obtain a water-based binder;
the polymerization degree of the polyvinyl alcohol in the step (1) is 1000-6000;
the molar ratio of the compound B to the polyvinyl alcohol monomer in the step (2) is (0.0005-10): 1;
the molar ratio of the acrylic monomer or the acrylic monomer and olefin monomer composition to the polyvinyl alcohol monomer in the step (2) is (0.003-80): 1;
the mass of the acrylic monomer in the acrylic monomer and olefin monomer composition in the step (2) accounts for 0.1-100% of the total mass of the composition, excluding 100%;
wherein the structure of the compound A is shown as the formula I:
wherein R is 1 Is absent or is a linear or branched alkylene group of C1-C4, R 2 Is amino, hydroxyl,
The structure of the compound B is shown as a formula II:
R 3 is phenyl or methyleneoxy.
2. The aqueous binder of claim 1, wherein the olefin monomer comprises any one of or a combination of at least two of a sulfonic acid-based monomer, a carboxyl-based monomer, or an amino-based monomer.
3. The aqueous binder of claim 2, wherein the sulfonic acid group alkenyl monomer comprises any one or a combination of at least two of sodium styrene sulfonate, sodium vinyl sulfonate, sodium allyl sulfonate, sodium 2-methyl allyl sulfonate, sodium ethyl methacrylate sulfonate, or 2-acrylamide-2-methylpropanesulfonic acid.
4. The aqueous binder of claim 2, wherein the carboxyl alkenyl monomer comprises any one of fumaric acid, methacrylic acid, itaconic acid, or monobutyl itaconate, or a combination of at least two thereof.
5. The aqueous binder of claim 2 wherein the amino-alkenyl monomer comprises any one or a combination of at least two of acrylamide, methacrylamide, N-methylolacrylamide or N, N-dimethylacrylamide.
6. A method for preparing an aqueous binder according to any one of claims 1 to 5, characterized in that it comprises the following steps:
(1) mixing the polyvinyl alcohol solution with an aqueous solution of an alkaline substance, adding the compound A for reaction, and cooling to obtain a water-solubility-enhanced polyvinyl alcohol solution;
(2) mixing the water-soluble enhanced polyvinyl alcohol solution obtained in the step (1) with a compound B and an acrylic monomer or a composition of the acrylic monomer and an olefin monomer for reaction, adding an initiator and continuing to react to obtain a water-based binder;
wherein the structure of the compound A is shown as the formula I:
wherein R is 1 Is absent or is a linear or branched alkylene group of C1-C4, R 2 Is amino, hydroxyl,
The structure of the compound B is shown as a formula II:
R 3 is phenyl or methyleneoxy;
the polymerization degree of the polyvinyl alcohol in the step (1) is 1000-6000;
the molar ratio of the compound B to the polyvinyl alcohol monomer in the step (2) is (0.0005-10): 1;
the molar ratio of the acrylic monomer or the acrylic monomer and olefin monomer composition to the polyvinyl alcohol monomer in the step (2) is (0.003-80): 1;
the mass of the acrylic monomer in the acrylic monomer and olefin monomer composition in the step (2) accounts for 0.1-100% of the total mass of the composition, excluding 100%.
7. The method according to claim 6, wherein the degree of alcoholysis of the polyvinyl alcohol in the step (1) is 60 to 99.99%.
8. The method according to claim 7, wherein the degree of alcoholysis of the polyvinyl alcohol in the step (1) is 80 to 99.99%.
9. The preparation method according to claim 6, wherein the mass fraction of the polyvinyl alcohol in the polyvinyl alcohol solution in the step (1) is 5-45%.
10. The method according to claim 6, wherein the basic substance in the step (1) is lithium hydroxide and/or sodium hydroxide.
11. The method according to claim 6, wherein the mass fraction of the alkaline substance in the aqueous alkaline substance solution in the step (1) is 0.1 to 15%.
12. The preparation method according to claim 6, wherein the molar ratio of the basic substance to the polyvinyl alcohol monomer in the step (1) is (0.005-10): 1.
13. The method according to claim 6, wherein the mixing temperature in step (1) is 25 to 60 ℃.
14. The method according to claim 6, wherein the mixing in step (1) is carried out under stirring.
15. The preparation method according to claim 14, wherein the stirring time is 0.5 to 3 hours.
16. The preparation method according to claim 6, wherein the molar ratio of the compound A to the polyvinyl alcohol monomer in the step (1) is (0.005-100): 1.
17. The method according to claim 6, wherein the temperature of the reaction in the step (1) is 60 to 90 ℃.
18. The preparation method according to claim 6, wherein the reaction time in the step (1) is 0.5-10 h.
19. The preparation method according to claim 6, wherein the temperature in the step (1) is reduced to 30-60 ℃.
20. The method according to claim 6, wherein the temperature of the mixing reaction in the step (2) is 30 to 60 ℃.
21. The preparation method according to claim 6, wherein the mixing reaction time in the step (2) is 0.5-6 h.
22. The method according to claim 6, wherein the initiator in the step (2) is an inorganic peroxide initiator and/or a redox initiator.
23. The method of claim 22, wherein the inorganic peroxide initiator comprises any one of ammonium persulfate, sodium persulfate, or potassium persulfate, or a combination of at least two thereof.
24. The method of claim 22, wherein the redox initiator is a combination of ammonium persulfate and sodium sulfite or a combination of ammonium persulfate and sodium bisulfite.
25. The method according to claim 6, wherein the initiator used in the step (2) is added in an amount of 0.0001 to 1.5% by mass based on the mass of the acrylic monomer or the combination of the acrylic monomer and the olefin monomer.
26. The preparation method according to claim 6, wherein the temperature for continuing the reaction after adding the initiator in the step (2) is 30 to 90 ℃.
27. The preparation method of claim 26, wherein the time for continuing the reaction after adding the initiator in the step (2) is 0.5-18 h.
28. Use of the aqueous binder according to any one of claims 1 to 5 for the preparation of lithium ion batteries.
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| PCT/CN2019/075803 WO2019242318A1 (en) | 2018-06-20 | 2019-02-22 | Waterborne binder, preparation method therefor and use thereof |
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| CN113563531B (en) * | 2020-04-28 | 2023-10-13 | 成都翊昂科技有限公司 | Graft copolymer aqueous binder, preparation method and application thereof in silicon carbon negative electrode |
| CN111668490B (en) * | 2020-06-18 | 2021-11-23 | 江苏卓高新材料科技有限公司 | Water-based binder, preparation method and application thereof |
| CN113889621B (en) * | 2020-07-01 | 2023-07-14 | 比亚迪股份有限公司 | Binder, negative electrode and lithium ion battery |
| CN114242990B (en) * | 2021-11-22 | 2023-09-26 | 华南理工大学 | Polyvinyl alcohol/allyl copolymer interpenetrating network silicon-carbon negative electrode water-based binder and preparation method and application thereof |
| CN114335544B (en) * | 2022-01-05 | 2024-07-05 | 湖南大晶新材料有限公司 | Water-based binder, lithium ion battery negative electrode material and lithium ion battery |
| CN114335546B (en) * | 2022-03-07 | 2022-05-10 | 北京壹金新能源科技有限公司 | Binder for battery electrode and battery electrode |
| CN114669717B (en) * | 2022-03-29 | 2024-01-26 | 阳江市惠尔特新材料科技有限公司 | Modified silica sol and preparation method and application thereof |
| CN114605946B (en) * | 2022-04-15 | 2023-06-02 | 深圳市研一新材料有限责任公司 | Water-based adhesive and preparation method and application thereof |
| CN114975871B (en) * | 2022-06-30 | 2024-06-07 | 浙江新安化工集团股份有限公司 | Water-soluble compound conductive adhesive, preparation method thereof, silicon electrode and ion battery |
| CN115799513B (en) * | 2022-12-09 | 2024-04-16 | 江苏正力新能电池技术有限公司 | Adhesive, and preparation method and application thereof |
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| CN106207184A (en) * | 2016-08-03 | 2016-12-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of water adhesive for lithium ion battery and its production and use |
| CN106866846A (en) * | 2017-03-09 | 2017-06-20 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery aqueous binders and preparation method thereof and electrodes of lithium-ion batteries |
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| US9263746B2 (en) * | 2012-08-01 | 2016-02-16 | Samsung Sdi Co., Ltd. | Binder for electrode of lithium rechargeable battery and electrode for rechargeable battery comprising the same |
| US9963520B2 (en) * | 2014-12-26 | 2018-05-08 | Kuraray Co., Ltd. | Aqueous emulsion and adhesive in which same is used |
| CN105601822A (en) * | 2016-02-03 | 2016-05-25 | 常州市奥普泰科光电有限公司 | Preparation method of polar-monomer-modified acrylate charged pressure-sensitive adhesive microspheres |
| CN105885743B (en) * | 2016-04-06 | 2017-02-08 | 柳宇轩 | Modified polyvinyl-alcohol binding agent |
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| CN106207184A (en) * | 2016-08-03 | 2016-12-07 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of water adhesive for lithium ion battery and its production and use |
| CN106866846A (en) * | 2017-03-09 | 2017-06-20 | 深圳市贝特瑞新能源材料股份有限公司 | A kind of lithium ion battery aqueous binders and preparation method thereof and electrodes of lithium-ion batteries |
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